Bicyclic imides as herbicides

ABSTRACT

Compounds of Formula I are disclosed which are useful for controlling undesired vegetation ##STR1## wherein Q is ##STR2## and W, R A   m , R 4  -R 8  are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula I and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula I.

This application is a Sec. 371 application of PCT application number PCT/EP93/02413, filed 06 Sep. 1993, which is a continuation-in-part of U.S. application Ser. No. 07/942,800, filed 10 Sep. 1992, now abandoned.

DESCRIPTION

This invention relates to novel bicyclic imides; a method for their preparation; and their use as herbicides.

It has already been disclosed that certain heterocyclic imides (see EP-A 272 594, EP-A 493 323, EP-B 0 070 389, EP-B 0 104 532) can be employed as herbicides.

Now novel bicyclic imides have been found that exhibit markedly better herbicidal activity with excel-lent selectivity.

The subject of the present invention therefore comprises compounds of formula I ##STR3## wherein the bond linking C-7 and C-8 may be single or double; m is 1-7;

R^(A) can occupy one or more of the 2 or 6-8 positions and is independently selected from the group: hydroxy, halogen, CN, OR³, (C₁ -C₄)alkyl, S(O)_(n) R³, COR³, C(O)SR³ and C(O)NR¹¹ R¹² ; ##STR4## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₄)carboxy alkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₆)alkynyloxyalky, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈) trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O)(OR¹⁷)₂, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R⁴ is hydrogen or halogen;

R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ;

R⁶ is hydrogen, (C₁ -C₈)alkyl, (C₁ -C₈)haloalkyl. halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, C(O)SR¹⁰, C(O)NR¹¹ R¹², CHO, CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NO₂, CN, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ;

R⁷ and R³ are independently hydrogen, (C₁ -C₃)alkyl. (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R¹ and R⁸ together with the carbon to which they are attached may be C═O;

R⁹ is (C₁ -C₆)alkyl, (C₁ -C₆)haloalkyl, (C₂ -C₆)alkoxyalkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

R¹⁰ is (C₁ -C₈)alkyl. (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₃)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, (C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ p(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R¹², CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl and pyridyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl;

R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹² may be taken together: as --(CH₂)₅ --, --(CH₂)₄ -- or --CH₂ CH₂ OCH₂ CH₂ --, in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl;

R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C₈)cycloalkyl;

R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl;

R¹⁶ is hydrogen or (C₁ -C₃)alkyl

R¹⁷ is (C₁ -C₆)alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

W is O or S;

n is O or 2; provided that when Q is not fused to a ring bridging the 5'- and 6═-position and C-7 and C-8 are linked by a single bond, then at least one R^(A) is other than hydroxy, halogen, (C₁ -C₄)alkyl and (C₁ -C₄)alkoxy.

The subject of the present invention comprises further bicyclic imides selected from the group consisting of 4-[4'-chloro-2'-fluoro-5'-(prop-2- ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo-[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(2-propynyloxy)phenyl]-3,5-dioxo-7-chloro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-ethoxy)phenyl]-3,5-dioxo-7,7-difluoro-1,4-diazabicyclo[3.3.0]octane and stereoisomers thereof.

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", includes straight Chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers. Alkoxy includes e.g. methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy isomers. Alkenyl includes straight chain or branched alkenes, e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl isomers. Cycloalkyl includes e.g. cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen", either alone or in compound words such as "haloalkyl", means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂ CH₂ F, CF₂ CF₃ and CH₂ CHFCl.

More preferred are compounds of formula I having at least one of the following specifications

R³ is p referred (C₁ -C₄)alkyl, (C₃ -C₆)cycloalkyl, (C₃ -C₆)alkenyl, (C₃ -C₆)alkynyl, (C₁ -C₄)haloalkyl, (C₂ -C₆)alkoxyalkyl: (C₂ -C₄)carboxyalkyl, (C₃ -C₆)alkoxycarbonylalkyl, (C₄ -C₆)alkenyloxyalkyl, (C₁ -C₆)alkynyloxyalkyl, (C₃ -C₆)haloalkoxyalkyl, (C₃ -C₆)trialkylsilyl, (C₃ -C₆)cyanoalkyl, (C₃ -C₆)haloalkenyl, (C₃ -C₆)haloalkynyl, (C₂ -C₆)alkylcarbonyl, P(O)(OR¹⁷)₂, (C₂ -C₆)alkoxycarbonyl, (C₂ -C₆)haloalkoxycarbonyl, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R⁵ is halogen or CN;

R⁶ is hydrogen, (C₁ -C₄)alkyl, (C₁ -C₄)haloalkyl, halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, CO₂ R¹⁰, C(O)SR¹⁰, C(O)NR¹¹ R¹², CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NHSO₂ R¹⁵ or NHSO NHR¹⁵ ;

R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O;

R⁹ is (C₁ -C₄)alkyl, (C₁ -C₄)haloalkyl, (C₂ -C₄)alkoxyalkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

R¹⁰ is (C₁ -C₄)alkyl, (C₃ -C₆)cycloalkyl, (C₃ -C₆)alkenyl, (C₃ -C₆)alkynyl, (C₁ -C₄)haloalkyl, (C₂ -C₄)alkoxyalkyl, (C₂ -C₄)alkylthioalkyl, (C₂ -C₄)alkylsulfinylalkyl, (C₂ -C₄)alkylsulfonylalkyl, (C₃ -C₆)alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₆)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₁ -C₆)alkenyloxyalkyl, (C₄ -C₆)alkynyloxyalkyl, (C₃ -C₆)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₆)alkenylthioalkyl, (C₁ -C₆)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₄)cyanoalkyl, (C₃ -C₆)halocycloalkyl, (C₃ -C₆)haloalkenyl, (C₅ -C₆)alkoxyalkenyl, (C₅ -C₆)haloalkoxyalkenyl, (C₅ -C₆)alkylthioalkenyl, (C₃ -C₆)haloalkynyl, (C₅ -C₆)alkoxyalkynyl, (C₅ -C₆)haloalkoxyalkynyl, (C₅ -C₆)alkylthioalkynyl, (C₂ -C₄)alkyl carbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ P(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R¹², CHR¹⁶ C(O)NH₂, (C₁ -C₂)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen. (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₂)alkyl or (C₁ -C₂)haloalkyl; or phenyl and pyridyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹² and R¹⁴ are independently (C₁ -C₂)alkyl, phenyl optionally substituted with halogen. (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl or (C₁ -C₂)alkoxy;

R¹¹ and R¹² may be taken together as --(CH₂)₅ --, --(CH₂)₄ -- or --CH₂ CH₂ OCH₂ CH₂ --, each ring optionally substituted with (C₁ -C₂)alkyl, phenyl or benzyl;

R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C₆)cycloalky;

R¹⁷ is (C₁ -C₄)alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl.

Compounds having a substituted proline residue, particularly in 7-position, exibit a beneficial effect on undesired plants, preferred are fluoro, bromo or chloro.

Particularly preferred method of use employs compounds of formula II ##STR5## in which R¹ is halogen (C₁ -C₄)alkyl OR³, S(O)_(n) R³, COR³, CO₂ R³ C(O)SR³ C(O)NR¹¹ R¹² or CN;

R² is hydrogen, halogen, (C₁ -C₄)alkyl, OR³, S(O)_(n) R³, COR³, CO₂ R³ C(O)SR³ C(O)NR¹¹ R¹² or CN;

Especially preferred method of use employs compounds of formula II in which at least one of R¹ -R³ has the meaning

R¹ =hydrogen or (C₁ -C₄)alkyl;

R² =fluoro, chloro, bromo, OR³, S(O)_(n) R³, CO₂ R³, C(O)NR¹¹ R¹² or CN;

R³ =(C₁ -C₄)alkyl, (C₃ -C₆)cycloalkyl, (C₃ -C₆)alkenyl, (C₃ -C₆)alkynyl, (C₁ -C₄)haloalkyl or (C₃ -C₆)trialkylsilyl.

Most preferred method of use employ compounds of formula II with at least one of the following specifications

R¹ =hydrogen,

R² =fluoro, chloro, bromo or OR³,

R³ =(C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl,

and in Q

R⁴ is fluoro or chloro;

R⁵ is chloro;

R⁶ is OR¹⁰, CO₂ R¹⁰, NHSO₂ R¹⁰ or SR¹⁰ ;

R⁷ is hydrogen;

R⁸ is hydrogen or methyl;

R⁹ is (C₃ -C₄)alkenyl or (C₃ -C₄)alkynyl;

R¹⁰ is (C₁ -C₄)alkyl, (C₃ -C₆)cycloalkyl, (C₃ -C₆)alkenyl (C₃ -C₄)alkynyl, (C₁ -C₃)haloalkyl, (C₂ -C₄)alkoxyalkyl, (C₃ -C₆)alkoxycarbonylalkyl, (C⁶ -C⁸)alkenyloxycarbonylalkyl, (C⁶ -C⁸)alkynyloxycarbonylalkyl or (C¹ -C²)carboxyalkyl.

If not otherwise specified the invention relates to both the individual possible stereoisomers of formula I and II and also mixtures of the isomers. Stereoisomers exhibiting the 2R-configuration are preferred to others.

The 2R-configuration exhibits significantly better control, e.g. up to 8-fold, compared with the 2S-configuration on undesired plants.

Subject of the invention is also a method for preparing the novel bicyclic imides comprising:

(a) reacting a compound of formula III

    Q--NCO                                                     III

with a compound of formula IV ##STR6## wherein R═H or (C₁ -C₄)alkyl, and cyclizing the intermediate and a method for preparing bicyclic imides of formula Ia ##STR7## wherein the bond linking C-7 and C-8 may be single or double: m is 1-7;

R^(A) can occupy one or more of the 2 or 8-8 positions and is independently selected from the group: hydroxy, halogen, CN, OR³, (C₁ -C₄)alkyl. S(O)_(n) R³, COR³, C(O)SR³ and C(O)NR¹¹ R¹² ;

Q is ##STR8## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈)trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O)(OR¹⁷)₂, CHR¹⁶ P(O)IOR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl. (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R⁴ is hydrogen or halogen;

R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ;

R⁶ is hydrogen, (C₁ -C₈)alkyl, (C₁ -C₈)haloalkyl, halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, C(O)SR¹⁰, C(O)NR¹¹ R¹², CHO, CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NO₂, CN, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ;

R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O;

R⁹ is (C₁ -C₈)alkyl, (C₁ -C₆)haloalkyl, (C₂ -C₆)alkoxyalkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

R¹⁰ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, (C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁵ p(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R¹², CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl and pyridyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl;

R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹² may be taken together as --(CH₂)₅ --, --(CH₂)₄ -- or --CH₂ CH₂ OCH₂ CH₂ --, in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl;

R¹³ and R¹⁴ may be taken together with the carbon to which they are art ached to form (C₃ -C₈)cycloalkyl;

R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl;

R¹⁶ is hydrogen or (C₁ -C₈)alkyl;

R¹⁷ is (C₁ -C₆)alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

W is O or S;

n is 0, 1 or 2;

selected from the group consisting ;of (b) or (c):

(b) reacting a compound of formula IV, wherein R═H or (C₁ -C₄)alkyl, with phosgene and then with an amine of formula VI

    Q--NH.sub.2                                                VI

to form compounds of formula VII, ##STR9## and cyclizing the compounds of formula VII, or

(c) reacting a compound of formula III with a compound of formula VIII ##STR10## to form a compound of formula IX, ##STR11##

and hydrolyzing and cylizing the compound of formula IX.

The novel bicyclic imides can be produced in a method comprising preparing a compound of formula II ##STR12## wherein R¹ is R^(A)

R² is R^(A) and H

comprising reacting a compound of formula X, ##STR13## wherein R═H or (C₁ -C₄)alkyl, with a compound of general formula III

    Q--NCO                                                     III

and converting the reaction product formed thereby.

Subject of the invention is further a method for making compounds of formula Ia ##STR14## wherein the bond linking C-7 and C-8 may be single or double; m is 1-7;

R^(A) can occupy one or more of the 2 or 6-8 positions and is independently selected from the group: hydroxy, halogen, CN, OR³, (C₁ -C₄)alkyl, S(O)_(n) R³, COR³, C(O)SR³ and C(O)NR¹¹ R¹² ;

Q is ##STR15## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈)trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O)(OR¹⁷)₂, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R⁴ is hydrogen or halogen;

R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ;

R⁶ is OR¹⁰, S(O)_(n) R¹⁰, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ;

R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O;

R⁹ is (C₁ -C₆)alkyl, (C₁ -C₆)haloalkyl, (C₂ -C₆)alkoxyalkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

R¹⁰ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈) cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₄ -C₈ )alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈) haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, (C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ P(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R¹², CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl and pyridyl optionally substituted with halogen. (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl;

R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹² may be taken together as --(CH₂)₅ --, --(CH₂)₄ -- or --CH₂ CH₂ OCH₂ CH₂ --, in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl;

R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C₈)cycloalkyl;

R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl;

R¹⁶ is hydrogen or (C₁ -C₃)alkyl;

R¹⁷ is (C₁ -C₆)alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

W is 0 or S;

n is 0, 1 or 2:

comprising reacting a compound of the formula XlII ##STR16## wherein Y=0, S, NH with a halide selected from the group R¹⁰ --Z, R¹⁵ SO₂ --Z, and R¹⁵ NHSO₂ --Z wherein Z is chlorine, bromine or iodine.

The novel bicyclic imides of general formula I are obtained in accordance with the invention by a general method A if arylisocyanates of general formula III

    Q--N═C═O                                           III

in which R⁴ to R¹⁷ have the meanings; indicated above, and proline carboxylic acids (esters) of general formula IV ##STR17## in which m and R^(A) have the meaning Indicated above and R═H or (C₁ -C₄)alkyl or active ester such as 0-succimid esters or anhydride esters are reacted in accordance with method A, optionally in the presence of an acid acceptor and optionally in the presence of a solvent.

A further subject of the invention is a method B for the preparation of compounds of formula I, which is outlined in what follows and m and R^(A) have the meanings indicated above. Therefor a compound of formula IV, wherein R═H or (C₁ -C₄)alkyl, is reacted with phosgene or a phosgene substituted [e.g., triphosgene (CCl₃ O)₂ C═O], first to compounds of formula V. Compounds of formula V are then reacted with compounds of formula VI to form compounds of formula VII. Subsequent cyclization forms compounds formula I. ##STR18##

A further subject of the invention is method C for the preparation of compounds of formula I, which is outlined in what follows and m and R^(A) have the meanings indicated above, where a compound of formula III is reacted with a compound of formula VIII, optionally in the presence of an acid acceptor and optionally in the presence of a solvent, to a compound of formula IX, and the compound IX so obtained is then hydrolysed and cyclized to compounds of formula I. ##STR19## A further subject of the invention is method D for the preparation of compounds of formula II, which is outlined in what follows and R¹ and R² have the meaning indicated above. Therefor a compound of general formula X, wherein R═H or (C₁ -C₄)alkyl, is reacted with a compound of general formula III, yielding a compound of general formula XI. Compounds of general formula XI are cyclized to compounds of general formula XII and converted to compounds of formula II. ##STR20##

A further subject of the invention is a method E for the preparation of compounds of formula I by reacting compounds of general formula XIII ##STR21## wherein m, R^(A), and R⁵ have the meaning indicated above and Y=0, S, NH with a halide of the formula XIV, XV or XVI,

    R.sup.10 --Z                                               XIV

    R.sup.15 SO.sub.2 --Z                                      XV

    R.sup.15 NHSO.sub.2 --Z                                    XVI

wherein Z is a chlorine-, bromine--or an iodine atom and R¹⁰ and R¹⁵ have the meanings indicated above.

In method A, the reaction for R=alkyl takes place in an inert organic solvent, for example in an aromatic solvent such as toluene, chlorobenzene, a halogenated hydrocarbon such as chloroform, methylene chloride, an ether such as diisopropyl ether, or in acetonitrile or dimethylformamide, optionally with base catalysis preferred at temperatures of 20° to 120° C. Preferably used as bases are organic bases, for example organic amines such as triethylamine or also pyridine (see EP-A 0 272 594).

For R═H, the reaction takes place in water as solvent or, preferably, in the two-phase system water organic solvent. Especially preferred is the mode of operation in which compounds of formula IV, optionally salts of IV, is added together in water with an inorganic base, for example an alkali or alkaline-earth metal hydroxide, carbonate or hydrogen carbonate, such as sodium hydroxide or also potassium carbonate, or an organic base, for example an organic amine such as triethylamine, and then compounds of formula IlI, dissolved in an inert solvent such as, for example toluene, chlorobenzene or chloroform is added. The reaction mixture is then held advantageously at temperatures between -40° C. to +120° C. preferably -10° C. to +40° C., up to several days, preferably between 3 and 50 h.

The aqueous phase is then adjusted to a pH value between 1 and 3 with acid, preferably with an inorganic acid such as aqueous hydrochloric acid or aqueous sulfuric acid. The ureas of formula VII thus formed are then cyclized at temperatures between 50° and 100° C. or, optionally, in the presence of an acid such as hydrochloric acid and/or hydroformic acid or, optionally by conversion to an ester (R=alkyl) by know methods (see Houben-Weyl, "Methoden der organischen Chemie" [Methods of Organic Chemistry], Vol. XV (1974)).

In method D, the reaction for R═H and (C₁ -C₄)alkyl takes place analogous to method A to give compounds formula XII. Known methods (see Houben-Weyl, "Methoden der organischen Chemie" [Methods of Organic Chemistry] Vol. EP-B 0 078 191) and standard chemistry (see Advanced Organic Chemistry, Jerry March, second edition 1977) leads to compounds of formula II.

The compounds of formula III are known or can be prepared by analogy with known methods; see Houben-Weyl, "Methoden der organisthen Chemie" [Methods of Organic Chemistry], Vol. VIII, p. 120 (1952), Houben-Weyl, Vol. IX, pp. 875, 869 (1955); EP-B 0 070 389 US-A 4 881 967; EP-A 0 322 401; US-A 3 495 967; EP-A 0 300 307; EP-A 0 349 832.

Compounds of general formula IV or X are commercially available or prepared according to methods described in the literature (e.g. S. Kanenasa et al., J. Org. Chem. 56, 2875 (1991); P. Beaulien et al., J. Chem. Soc. Perkin. Trans. I 11, 2885 (1991): R. M. Kellog et al., Tetrahedron Lett. 32(30), 3727 (1991) and many more). Houben-Weyl. Vol. XXV/1 and XXV/2 (1974). The latter literature describes also the active esters.

Amines of general formula VIII are known or can be prepared in accordance with EP-A 0 073 569 or in an analogous fashion in accordance witch the method described there.

The 2R-configuration can be achieved starting from the corresponding optically active proline or proline derivatives analogous to the methods specified above.

Finally, it was found that the bicyclic imides of general formula I and II exhibit outstanding herbicidal qualities.

A further subject of the invention is a composition for controlling weeds comprising an effective amount of at least one of the novel bicyclic imides and at least one carrier therefor.

A further subject of the invention is a method for controlling weeds comprising applying to the locus to be protected an effective amount of at least one of the novel bicyclic imides.

A further subject of the invention is a method for controlling weeds in plantation crops and peanut comprising applying to the locus to be protected an effective amount of a compound of formula Ia: ##STR22## wherein the bond linking C-7 and C-8 may be single or double; m is 1-7;

R^(A) can occupy one or more of the 2 or 6-8 positions and is independently selected from the group: hydroxy, halogen, CN, OR³, (C₁ -C₄)alkyl, S(O)_(n) R³, COR³, C(O)SR³, and C(O)NR¹¹ R¹² ;

Q is ##STR23## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₄)carboxy alkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈)trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O)(OR¹⁷)₂, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R⁴ is hydrogen or halogen;

R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ;

R⁶ is hydrogen, (C₁ -C₈)alkyl, (C₁ -C₈)haloalkyl, halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, C(O)SR¹⁰, C(O)NR¹¹ R¹², CHO, CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NO₂, CN, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ;

R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O;

R⁹ is (C₁ -C₆)alkyl, (C₁ -C₆)haloalkyl, (C₂ -C₆)alkoxyalkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

R¹⁰ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₁ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₁ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, (C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ P(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ IR¹², CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl and pyridyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl;

R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy;

R¹¹ and R¹² may be taken together as --(CH₂)₅ --, --(CH₂)₄ -- or --CH₂ CH₂ OCH₂ CH₂ --, in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl;

R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C₈)cycloalkyl;

R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl;

R¹⁶ is hydrogen or (C₁ -C₃)alkyl;

R¹⁷ is (C₁ -C₆)alkyl; (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl;

W is 0 or S;

n is 0, 1, or 2.

In this method is preferred the plantation crop selected from the group consisting of citrus, sugarcane, coffee, banana, oil palm, grapes and rubber. Further is preferred employing at least one of the compounds of the group consisting of 4-[4'-chloro-2'-fluoro-5'-(1-methylethoxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-ethoxy)phenyl]-3,5-dioxo-7,7-difluoro-1,4-diazabicyclo[3.3.0]octane, 2-(7-fluoro-3-oxo-4-prom-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-tetrahydro-pyrrolo[1,2c]imidazole-1,3-dione, 6,6-difluoro-2-(7-fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1.4]oxazin-6-yl)tetrahydropyrrolo[1,2-c]imidazole-1,3-dione (JUPAC), 4-[2-chloro-4-fluoro-5-(6-fluoro-1,3-dioxotetrahydropyrrolo[1,2-c]imidazol-2-yl)phenoxy]but-2-enoic acid methyl ester (JUPAC) and stereoisomers thereof. Preferred is also a method in which the crop is peanut and the compound is applied preemergence.

Chemical examples EXAMPLE 1 ##STR24##

A mixture of 2(R)-Carbomethoxy-4-fluoropyrrolidine (1,47 g, 0,01 ml), triethylamine (50,0 mg, 0,5 mmol) and toluene (30 ml) is prepared, and 4-chloro-2-fluoro-5-isopropoxyphenyl isocyanate (2,29 g, 0,01 mol) dissolved in toluene (20 ml) is added dropwise. The reaction mixture is stirred for 5 h at reflux, then washed with 10% aqueous hydrochloric acid (3×10 ml) and water (3×10 ml), dried over sodium sulfate, and filtered. After concentration of the filtrate by evaporation, the resulting residue is purified by silica gel chromatography.

2R-4-(4'-Chloro-2 -fluoro-5'-isopropoxyphenyl)-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane is obtained in the amount of 2.58 g (75% theoretical) as colourless crystals (m.p. 103°-105° C.).

EXAMPLE 2 ##STR25##

2R-4-(4'-chloro-2'-fluoro-5'-carboisopropoxy)-3,5-dioxo-7-hydroxy-1,4-diazabicyclo[3.3.0]octane 3.71 g (0.01 mol) is dissolved in toluene (30 ml) and cooled to 0°-5° C., before thionyl chloride (1.44 g, 12.0 mmol) in toluene (10 ml) is added dropwise. The reaction mixture is refluxed for 15 h. The solvent and the excess of thionyl chloride is evaporated and the residue is purified by silica gel chromatography,

2R-4-(4'-chloro-2'-fluoro-5'-carboisopropoxy)-7-chloro-3,5-dioxo-1,4-diazabicyclo[3.3.0] octane is obtained in the amount of 3,19 g (82% of theoretical) as a colorless glass.

EXAMPLE 3 ##STR26##

A mixture or 2R-4-(4-chloro-2-fluoro-5'-carboisopropoxyphenyl)-3,5-dioxo-7-hydroxy-1,4-diazabicyclo[3.3.0]octane (3.71 g, 0,01 mol), triethylamine (1,41 g. 14.0 mol) and acetic acid anhydride (1.24 g, 12.0 mmol) are added together in methylene chloride (30 ml) and toluene (60 ml). The reaction mixture is refluxed for 13 h. cooled to room temperature and the organic layer is washed with water (3×15 ml). The collected organic layers are dried over sodium sulfate, and filtered. After concentration of the filtrate by evaporation, the resulting residue is purified by silica gel chromatography.

2R-4-(4'-Chloro-2 -fluoro-.5 -isopropoxyphenyl)-3,5-dioxo-7-methylcarbonyloxy-1,4-diazabicyclo[3.3.0]octane is obtained in the amount of 2.84 g (69% of theoretical) as a colourless glass.

EXAMPLE 4 ##STR27##

A mixture of 4-(4-(4-Chloro-2'-fluoro-5 -hydroxyphenyl)-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane (3,03 g, 0.01 mol), potassium carbonate (6.95 g, 0,05 mol) propargyl bromide (1,78 g, 12.0 mmol) and acetonitrile (60 ml) is stirred for 20 h at 20° C. The reaction mixture is acidified to pH=2 with 5% aqueous hydrochloric acid, followed by extraction with ether (3×15 ml). The ether layer is dried over sodium sulfate, and filtered. After evaporation of the solvent, the residue is purified by silica gel chromatography.

4-(4'-Chloro-2-fluoro-5-propargyloxyphenyl)-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0] octane is obtained in the amount of 3,16 g (93% of theoretical) in two fractions as, two diastereomers (or diastereomeric mixtures).

1. Fraction: m.p. 136°-139° C. [α]_(D) ²⁰ =+45.1° C.

2. Fraction: m.p. 143°-145° C. [α]_(D) ²⁰ =-35.2° C.

Analogously to Example 1 to 4 and in accordance with the general discription of the methods A to E in accordance with the invention, the compounds of general formula I lasted in the following tables can be prepared:

                  TABLE 1                                                          ______________________________________                                          ##STR28##                                                                                                        melting                                     R.sup.A                                                                               R.sup.4  R.sup.5                                                                               R.sup.6     point °C.                            ______________________________________                                         H      7-F      Cl     H                                                       H      8-F      Cl     H                                                       H      7-Cl     Cl     CO.sub.2 CH(CH.sub.3).sub.2                             H      8-Cl     Cl     OCH(CH.sub.3).sub.2                                     H      6-F      Cl                                                                                     ##STR29##                                              H      7-Br     Cl                                                                                     ##STR30##                                              ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________      ##STR31##                                                                                                   melting                                          R.sup.1                                                                               R.sup.2                                                                          R.sup.4                                                                          R.sup.5                                                                           R.sup.6         point °C.                                 __________________________________________________________________________     F      H H Cl H                                                                F      H H Br H                                                                F      H H CH.sub.3                                                                          H                                                                F      H F Cl H                                                                F      H Cl                                                                               Cl H                                                                F      H F Cl OCH(CH.sub.3).sub.2                                                                            91-93 (R/S-Mixture                                                             at Pos. 2 and 7)                                 F      H F Cl OCH(CH.sub.3).sub.2                                                                            103-105 (2R, 7S-Konfi-                                                         guration, [α].sub.D.sup.20 = +48,8                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                  F      H F Cl OCH(CH.sub.3).sub.2                                                                            glass (2R, 7R-Konfi-                                                           guration, [Ε].sub.D.sup.20 = +38,3                                     (c = 1 in CH.sub.3 OH))                          F      H F Cl OCH(CH.sub.3).sub.2                                                                            glass                                            F      H F Cl                                                                                 ##STR32##      143-145 (2S, 7R/S-Konfi-                                                       guration, [α].sub.D.sup.20 = -35,2                                       (c = 0,5 in CH.sub.3 OH))                        F      H F Cl                                                                                 ##STR33##      136-139 (2R, 7R/S-Konfi-                                                       guration, [α].sub.D.sup.20 = +45,1                                       (c = 0,5 in CH.sub.2 OH))                        F      H F Cl                                                                                 ##STR34##      glass (2R/S, 7R/S-Konfi-                                                       guration)                                        F      H F Cl                                                                                 ##STR35##      133-139 (2S, 7R/S-Konfi-                                                       guration, [α].sub.D.sup.20 = -29,9                                       (c = 0,5 in CH.sub.3 OH))                        F      H F Cl                                                                                 ##STR36##      121-124 (2R, 7R/S-Konfi-                                                       guration, [α].sub.D.sup.20 = +41,5                                       (c = 0,5 in CH.sub.3 OH))                        F      H F Cl                                                                                 ##STR37##      glass (2R/S, 7R/S-Konfi-                                                       guration)                                        F      H F Cl OCH.sub.3                                                        F      H F Cl OCH.sub.2 CH.sub.2 CH.sub.3                                      F      H F Cl OCH.sub.2 CHCH.sub.2                                             F      H F Cl OCH.sub.2 CHCHCO.sub.2 CH.sub.3                                                                glass                                            F      H F Cl OCH.sub.2 CO.sub.2 CH.sub.3                                      F      H F Cl                                                                                 ##STR38##                                                       F      H F Cl OCH.sub.2 CO.sub.2 C.sub.5 H.sub.11                              F      H F Cl CN                                                               F      H F Cl SCH.sub.3                                                        F      H F Cl SCH(CH.sub.3).sub.2                                              F      H F Cl SCH.sub.2 CHCH.sub.2                                             F      H F Cl                                                                                 ##STR39##                                                       F      H F Cl SCH.sub.2 CO.sub.2 H                                             F      H F Cl SCH.sub.2 CO.sub.2 CH.sub.3                                      F      H F Cl                                                                                 ##STR40##                                                       F      H F Cl OC(CH.sub.3)NOCH.sub.3                                           F      H F Cl                                                                                 ##STR41##                                                       F      H F Cl OCHF.sub.2                                                       F      H F Cl OCH.sub.2 C(Cl)CH.sub.2                                          F      H F Cl OCF.sub.2 CHFCl                                                  F      H F Cl NHSO.sub.2 CH.sub.3                                              F      H F Cl NHSO.sub.2 CH(CH.sub.3).sub.2                                    F      H F Cl NHSO.sub.2 NHCH.sub.3                                            F      H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7R/S-Konfi-                                                           guration, [α].sub.D.sup.20 = +32,4                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                  F      H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                              F      H F Cl CO.sub.2 CH.sub.2 CF.sub.3                                       F      H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R/S, 7R/S-Konfi-                                                         guration)                                        F      H F Cl CO.sub.2 N(CH.sub.3).sub.2                                       F      H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                           F      H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3                                    F      H F Cl                                                                                 ##STR42##                                                       F      H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 SCH.sub.3                          Cl     H F Cl H                                                                Cl     H F Cl OCHF.sub.2                                                       Cl     H F Cl OCH(CH.sub.3).sub.2                                                                            oil (2R, 7S-Konfi-                                                             guration, [α].sub.D.sup.20 = +41,7                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                  Cl     H F Cl OCF.sub.2 CHFCl                                                  Cl     H F Cl                                                                                 ##STR43##      oil (2R, 7S-Konfi-                                                             guration, [α].sub.D.sup.20 = -35,8                                       (c = 0,5 in CH.sub.3 OH))                        Cl     H F Cl                                                                                 ##STR44##      glass (2R, 7S-Konfi-                                                           guration)                                        Cl     H F Cl                                                                                 ##STR45##      glass (2R/S, 7S-Konfi-                                                         guration)                                        Cl     H F Cl OCH.sub.2 P(O)(C.sub.2 H.sub.5).sub.2                            Cl     H F Cl                                                                                 ##STR46##      oil (2R, 7S-Konfi-                                                             guration)                                        Cl     H F Cl                                                                                 ##STR47##      130-145 (2S, 7S-Konfi-                                                         guration, [α].sub.D.sup.20 = -27,3                                       in CH.sub.3 OH))                                 Cl     H F Cl OCH.sub.2 C(O)N(CH.sub.3).sub.2                                  Cl     H F Cl O(CH.sub.2).sub.2 OCH.sub.2 CH.sub.3                             Cl     H F Cl OCH.sub.2 CHNOCH.sub.2 CHCH.sub.2                                Cl     H F Cl                                                                                 ##STR48##                                                       Cl     H F Cl SCH.sub.2 CO.sub.2 H                                             Cl     H F Cl                                                                                 ##STR49##                                                       Cl     H F Cl NHSO.sub.2 CH.sub.3                                              Cl     H F Cl NHSO.sub.2 CF.sub.3                                              Cl     H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7S-Konfi-                                                             guration, [α].sub.D.sup.20 = +36,6                                       (c = 0,5 in CH.sub.2 Cl))                        Cl     H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 SCH.sub.3                          Cl     H F Cl CO.sub.2 CH(CH.sub.3)CF.sub.3                                    Cl     H F Cl CO.sub.2 N(CH.sub.3).sub.2                                       Cl     H F Cl                                                                                 ##STR50##                                                       Cl     H F Cl                                                                                 ##STR51##                                                       Cl     H F Cl CO.sub.2 CH.sub.2 CF.sub.3                                       Cl     H F Cl                                                                                 ##STR52##                                                       Cl     H F Cl CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                             oil (2R, 7S-Konfi-                                                             guration)                                        Cl     H F Cl CHCHCO.sub.2 CH.sub.2 CH.sub.3                                   OSi(CH.sub.3).sub.3                                                                   H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7S-Konfi-                                                             guration, [α].sub.D.sup.20 = +29,5                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                  OSi(CH.sub.3).sub.3                                                                   H F Cl                                                                                 ##STR53##                                                       OSi(CH.sub.3).sub.3                                                                   H F Cl                                                                                 ##STR54##                                                       OC(O)CH.sub.3                                                                         H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7S-Konfi-                                                             guration)                                        OC(O)CH.sub.3                                                                         H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7R-Konfi-                                                             guration)                                        OC(O)CH.sub.3                                                                         H F Cl                                                                                 ##STR55##                                                       OCO.sub.2 CH.sub.3                                                                    H F Cl OCH(CH.sub.3).sub.2                                                                            oil (2R, 7S-Konfi-                                                             guration)                                        OCO.sub.2 CH.sub.3                                                                    H F Cl OCH(CH.sub.3).sub.2                                                                            oil (2R, 7R-Konfi-                                                             guration)                                        OSO.sub.2 CH.sub.3                                                                    H F Cl OCH(CH.sub.3).sub.2                                                                            140-141 (2R, 7R-Konfi-                                                         guration, [α].sub.D.sup.20 = +56,3                                       in CH.sub.2 Cl.sub.2))                           OCH.sub.3                                                                             H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    oil (2R, 7R-Konfi-                                                             guration, [α].sub.D.sup.20 = +55,1                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                  OCH.sub.3                                                                             H F Cl CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                              OCH.sub.3                                                                             H F Cl OCH(CH.sub.3).sub.2                                              OCH.sub.3                                                                             H F Cl                                                                                 ##STR56##                                                       OH     H F Cl OCH(CH.sub.3).sub.2                                                                            63-65 (2R, 7R/S-Konfi-                                                         guration, [α].sub.D.sup.20 = +47,1                                       (c = 0,5 in CH.sub.3 OH))                        OH     H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    45-48 (2S/7R/S-Konfi-                                                          guration)                                        OH     H H Cl H               161,5-63                                         OH     H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                                                    110-112 (2R/7R-Konfi-                                                          guration, [α].sub.D.sup.20 = +39,2                                       (c = 0,5 in CH.sub.3 OH)                         OCH.sub.3                                                                             H F Cl                                                                                 ##STR57##                                                        ##STR58##                                                                            H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                      CH.sub.3                                                                              H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                      CO.sub.2 H                                                                            H F Cl OCH(CH.sub.3).sub.2                                              CO.sub.2 H                                                                            H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                      Br     H F Cl CO.sub.2 CH(CH.sub.3).sub.2                                      Br     H F Cl CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                           Br     H F Cl OCHF.sub.2                                                       Br     H F Cl OCH(CH.sub.3).sub.2                                                                            oil (2R, 7S-Konfi-                                                             guration, [α].sub.D.sup.20 = +26,5                                       (c = 0,5 in CH.sub.2 Cl.sub.2)                   Br     H F Cl OCF.sub.2 CHF.sub.2                                              Br     H F Cl                                                                                 ##STR59##                                                       Br     H F Cl                                                                                 ##STR60##                                                       Br     H F Cl SCH.sub.2 CO.sub.2 H                                             Br     H F Cl NHSO.sub.2 CH.sub.3                                              Br     H F Cl NHSO.sub.2 CF.sub.3                                              F      F F Cl OCH(CH.sub.3).sub.2                                                                            99-101 (2R-Konfi-                                                              guration, [α].sub.D.sup.20 = -34,2                                       (c = 0,5 in CHCl.sub.3))                         F      F F Cl OCH.sub.2 CHCH.sub.2                                                                           glass                                            F      F F Cl OCF.sub.2 CHCH.sub.2                                                                           glass                                            F      F F Cl CO.sub.2 CH(CH.sub.3).sub.2                                      F      F F Cl SCH.sub.2 CO.sub.2 CH.sub.3                                      F      F F Cl                                                                                 ##STR61##                                                       F      F F Cl                                                                                 ##STR62##                                                       F      F Cl                                                                               Cl CO.sub.2 CH(CH.sub.3).sub.2                                      F      F Cl                                                                               Cl                                                                                 ##STR63##                                                       F      F Cl                                                                               Cl                                                                                 ##STR64##                                                       __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR65##                                                                                                melting                                             R.sup.1                                                                              R.sup.2                                                                          R.sup.4                                                                          R.sup.5                                                                             R.sup.7                                                                           R.sup.8                                                                               w point °C.                                    __________________________________________________________________________     F     H F Cl   H  CH.sub.2                                                                              O glass (2R/S, 7S-Konfi-                                                         guration)                                           F     H F Cl   H  CH.sub.3                                                                              O glass (2S, 7S-Konfi-                                                           guration, [α].sub.D.sup.20 = +19,5                                       (c = 0,5 in CH.sub.2 Cl.sub.2))                     F     H F Cl   H  CH.sub.3                                                                              O glass (2R, 7S-Konfi-                                                           guration, [α].sub.D.sup.20 = -16,6                                       (c = 0,5 in CH.sub.2 Cl.sub.2)                      F     H F Cl   H  H      O                                                     F     H F Cl   CH.sub.3                                                                          CH.sub.3                                                                              O                                                     F     H F Cl   CH.sub.3                                                                          CH.sub.2 F                                                                            O                                                     F     H F Cl   H  CH.sub.2 CH.sub.3                                                                     O                                                     F     H F Cl   H  CH.sub.2 F                                                                            O                                                     F     H F Cl   H  CH.sub.2 Cl                                                                           O                                                     F     H F Cl   H  CH.sub.2 Br                                                                           O                                                     F     H F Br   H  CH.sub.3                                                                              O                                                     F     H F CH.sub.3                                                                            H  CH.sub.3                                                                              O                                                     F     H F OCH.sub.3                                                                           H  CH.sub.3                                                                              O                                                     F     H F CN   H  CH.sub.3                                                                              O                                                     F     H F CF.sub.3                                                                            H  CH.sub.3                                                                              O                                                     F     F F Cl   H  CH.sub.3                                                                              O 151-154                                             F     F Cl                                                                               Cl   H  CH.sub.3                                                                              O                                                     F     H F OCF.sub.2 H                                                                         H  CH.sub.3                                                                              O                                                     F     H Cl                                                                               Cl   H  CH.sub.3                                                                              O                                                     Cl    H F Cl   H  CH.sub.3                                                                              O                                                     Cl    H Cl                                                                               Cl   H  CH.sub.3                                                                              O                                                     Cl    H F Cl   CH.sub.3                                                                          CH.sub.3                                                                              O                                                     Cl    H F Cl   CH.sub.3                                                                          CH.sub.2 F                                                                            O                                                     Cl    H F Cl   H  CH.sub.2 F                                                                            O                                                     Cl    H F Cl   H  CH.sub.2 Cl                                                                           O                                                     Cl    H F Cl   H  CH.sub.2 Br                                                                           O                                                     Cl    H F Cl   H  CH(CH.sub.3).sub.2                                                                    O                                                     Cl    H F Cl   H  CH.sub.2 CH.sub.2 Cl                                                                  O                                                     Cl    H F Cl   H  CH.sub.2 CH.sub.3                                                                     O                                                     Cl    H F Cl   H  CH.sub.2 (CH.sub.2).sub.2 F                                                           O                                                     Cl    H F Br   H  CH.sub.3                                                                              O                                                     Cl    H F CH.sub.3                                                                            H  CH.sub.3                                                                              O                                                     Cl    H F OCH.sub.3                                                                           H  CH.sub.3                                                                              O                                                     Cl    H F CN   H  CH.sub.3                                                                              O                                                     Cl    H F CF.sub.3                                                                            H  CH.sub.3                                                                              O                                                     Cl    H F OCF.sub.2 H                                                                         H  CH.sub.3                                                                              O                                                     OCH.sub.3                                                                            H F Cl   H  CH.sub.3                                                                              O                                                     OSi(CH.sub.3).sub.3                                                                  H F Cl   H  CH.sub.3                                                                              O                                                     CH.sub.3                                                                             H F Cl   H  CH.sub.3                                                                              O                                                     CO.sub.2 H                                                                           H F Cl   H  CH.sub.3                                                                              O                                                     Br    H F Cl   H  CH.sub.3                                                                              O                                                     Br    H F Cl   H  CH.sub.2 F                                                                            O                                                     Br    H F Cl   H  CH.sub.2 Br                                                                           O                                                     Br    H F Cl   CH.sub.3                                                                          CH.sub.3                                                                              O                                                     Br    H F Cl   CH.sub.3                                                                          CH.sub.2 F                                                                            O                                                     Br    H Cl                                                                               Cl   H  CH.sub.3                                                                              O                                                     __________________________________________________________________________

                  TABLE 4                                                          ______________________________________                                          ##STR66##                                                                                                                melting                             R.sup.1 R.sup.2                                                                              R.sup.4                                                                              R.sup.5                                                                               R.sup.7                                                                            R.sup.8 w   point °C.                    ______________________________________                                         F       H     F     Cl     H   Cl      S                                       F       H     F     Cl     H   CH.sub.3                                                                               S                                       F       H     F     Cl     H   CH.sub.2 CH.sub.3                                                                      S                                       F       H     H     SCH.sub.3                                                                             H   H       S                                       F       H     F     Cl     H   Cl      O                                       F       H     F     Cl     H   CH.sub.3                                                                               O                                       Cl      H     F     Cl     H   Cl      S                                       Cl      H     F     Cl     H   CH.sub.3                                                                               S                                       Cl      H     F     Cl     H   CH.sub.2 CH.sub.3                                                                      S                                       Cl      H     H     SCH.sub.3                                                                             H   H       S                                       Cl      H     F     Cl     H   Cl      O                                       Cl      H     F     Cl     H   CH.sub.3                                                                               O                                       OCH.sub.3                                                                              H     F     Cl     H   CH.sub.3                                                                               S                                       OCH.sub.3                                                                              H     F     Cl     H   Cl      S                                       Br      H     F     Cl     H   CH.sub.3                                                                               S                                       F       F     F     Cl     H   Cl      S                                       Br      H     F     Cl     H   Cl      S                                       Br      H     F     Cl     H   CH.sub.3                                                                               O                                       OSi(CH.sub.3).sub.3                                                                    H     F     Cl     H   CH.sub.3                                                                               S                                       ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                          ##STR67##                                                                                                            melting                                 R.sup.1  R.sup.2                                                                               R.sup.4                                                                               R.sup.9     w   point °C.                        ______________________________________                                         H        H      F                                                                                      ##STR68##  O                                           F        H      F      H           S                                           F        H      F      CH.sub.3    S                                           F        H      F      CH.sub.2 CH.sub.3                                                                          S                                           F        H      F                                                                                      ##STR69##  S                                           F        H      F      CH.sub.2 CHCH.sub.2                                                                        S                                           F        H      F      CH.sub.2 OCH.sub.2                                                                         S                                           F        H      F      CH.sub.2 CH.sub.2 CH.sub.3                                                                 S                                           F        H      F                                                                                      ##STR70##  S                                           F        H      F      CH(CH.sub.3).sub.2                                                                         S                                           F        H      F      CF.sub.2 CHF.sub.2                                                                         S                                           F        F      F                                                                                      ##STR71##  S                                           F        F      F      CH.sub.2 CHCH.sub.2                                                                        S                                           F        F      F      CH.sub.2 CO.sub.2 CH.sub.3                                                                 S                                           F        H      Cl                                                                                     ##STR72##  S                                           F        H      F                                                                                      ##STR73##  O                                           Cl       H      F      H           S                                           Cl       H      F      CH.sub.3    S                                           Cl       H      F      CH.sub.2 CH.sub.3                                                                          S                                           Cl       H      F      CH(CH.sub.3).sub.2                                                                         S                                           Cl       H      F      CH.sub.2 CH.sub.2 CH.sub.3                                                                 S                                           Cl       H      F                                                                                      ##STR74##  S                                           Cl       H      F                                                                                      ##STR75##  S                                           Cl       H      F                                                                                      ##STR76##  S                                           Cl       H      F      CF.sub.2 CHF.sub.2                                                                         S                                           Cl       H      F      CH.sub.2 CHCHCH.sub.3                                                                      S                                           Cl       H      Cl                                                                                     ##STR77##  S                                           OCH.sub.3                                                                               H      F                                                                                      ##STR78##  S                                           OCH.sub.3                                                                               H      F      CH.sub.3    S                                           Br       H      F                                                                                      ##STR79##  S                                           Br       H      F      CH.sub.3    S                                           Br       H      F                                                                                      ##STR80##  S                                           Br       H      F      CH.sub.2 CH.sub.3                                                                          S                                           Br       H      F      CH.sub.2 CH.sub.2 CH.sub.3                                                                 S                                           Br       H      Cl                                                                                     ##STR81##  S                                           Br       H      F                                                                                      ##STR82##  O                                           ______________________________________                                    

                                      TABLE 6                                      __________________________________________________________________________      ##STR83##                                                                                                melting                                             R.sup.1                                                                              R.sup.2                                                                          R.sup.4                                                                          R.sup.7                                                                           R.sup.8                                                                           R.sup.9  w point °C.                                    __________________________________________________________________________     F     H F H  H  CH.sub.3 O                                                     F     H F H  H  CH.sub.2 CH.sub.3                                                                       O                                                     F     H F H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              O                                                     F     H F H  H  CH(CH.sub.3).sub.2                                                                      O                                                     F     H F H  H                                                                                  ##STR84##                                                                              O 189-191 (2R, 7S-                                                               Konfiguration)                                      F     H F H  H  CH.sub.2 CCH.sub.2                                                                      O                                                     F     H F H  H                                                                                  ##STR85##                                                                              O                                                     F     H F CH.sub.3                                                                          H                                                                                  ##STR86##                                                                              O                                                     F     H Cl                                                                               H  H                                                                                  ##STR87##                                                                              O                                                     F     H F H  H                                                                                  ##STR88##                                                                              S                                                     OH    H F H  H                                                                                  ##STR89##                                                                              O 207-209                                             F     H F CH.sub.3                                                                          CH.sub.3                                                                           ##STR90##                                                                              O                                                     Cl    H F H  H  H        O                                                     Cl    H F H  H  CH.sub.3 O                                                     Cl    H F H  H  CH.sub.2 CH.sub.3                                                                       O                                                     Cl    H F H  H                                                                                  ##STR91##                                                                              O                                                     Cl    H F H  H  CH(CH.sub.3).sub.2                                                                      O                                                     Cl    H F H  H                                                                                  ##STR92##                                                                              O                                                     Cl    H F H  H  CH.sub.2 CHCH.sub.2                                                                     O                                                     Cl    H F CH.sub.3                                                                          H                                                                                  ##STR93##                                                                              O                                                     Cl    H F CH.sub.3                                                                          CH.sub.3                                                                           ##STR94##                                                                              O                                                     Cl    H Cl                                                                               H  H                                                                                  ##STR95##                                                                              O                                                     Cl    H F H  H                                                                                  ##STR96##                                                                              S                                                     OCH.sub.3                                                                            H F H  H                                                                                  ##STR97##                                                                              O                                                     Br    H F H  H  CH.sub.3 O                                                     Br    H F H  H  CH.sub.2 CH.sub.2 CH.sub.3                                                              O                                                     Br    H F CH.sub.3                                                                          H                                                                                  ##STR98##                                                                              O                                                     Br    H F CH.sub.3                                                                          CH.sub.3                                                                           ##STR99##                                                                              O                                                     Br    H Cl                                                                               H  H                                                                                  ##STR100##                                                                             O                                                     Br    H Cl                                                                               H  H                                                                                  ##STR101##                                                                             S                                                     OSi(CH.sub.3).sub.3                                                                  H F H  H                                                                                  ##STR102##                                                                             O                                                     OSi(CH.sub.3).sub.3                                                                  H F H  H                                                                                  ##STR103##                                                                             S                                                     F     F F H  H                                                                                  ##STR104##                                                                             O glass (2R-                                                                     Konfigura-                                                                     tion)                                               F     F F H  H  CH.sub.2 CHCH.sub.2                                                                     O                                                     F     F F H  H  CH.sub.2 CO.sub.2 CH.sub.3                                                              O                                                     __________________________________________________________________________

                  TABLE 7                                                          ______________________________________                                          ##STR105##                                                                                                        melting                                    R.sup.1   R.sup.2 R.sup.4 R.sup.7                                                                              R.sup.8                                                                            point °C.                           ______________________________________                                         F         H       H       F     F                                              F         H       F       F     F                                              F         H       F       H     H                                              Cl        H       H       F     F                                              Cl        H       F       F     F                                              Cl        H       F       H     H                                              OCH.sub.3 H       H       F     F                                              OCH.sub.3 H       F       F     F                                              OCH.sub.3 H       F       H     H                                              Br        H       H       F     F                                              Br        H       F       F     F                                              Br        H       F       H     H                                              F         F       F       H     H                                              F         F       F       F     F                                              F         F       H       F     F                                              ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                          ##STR106##                                                                                                             melting                               R.sup.1                                                                              R.sup.2                                                                              R.sup.5                                                                              R.sup.6                                                                            R.sup.7       R.sup.8                                                                             point °C.                      ______________________________________                                         F     H     H     H   CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   Cl    H     H     H   CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   F     H     H     H   CO.sub.2 C.sub.2 H.sub.5                                                                     CH.sub.3                                   F     H     H     H   CO.sub.2 C.sub.2 H.sub.5                                                                     H                                          F     H     H     H   CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           CH.sub.3                                   Cl    H     H     H   CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           H                                          Cl    H     H     H   CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   F     H     H     H   CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           H                                          F     H     H     H                                                                                   ##STR107##   CH.sub.3                                   F     H     H     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   F     H     H     Cl  CO.sub.2 C.sub.2 H.sub.5                                                                     CH.sub.3                                   F     H     H     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           CH.sub.3                                   Cl    H     H     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   F     H     H     Cl                                                                                  ##STR108##   CH.sub.3                                   F     H     F     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   F     H     F     Cl  CO.sub.2 C.sub.2 H.sub.5                                                                     CH.sub.3                                   F     F     F     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   F     F     F     Cl  CO.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.3                                   F     F     F     Cl  CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                          CH.sub.3                                   F     F     F     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   F     F     Cl    Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   F     H     F     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           CH.sub.3                                   F     H     F     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           H                                          F     H     F     Cl                                                                                  ##STR109##   CH.sub.3                                   F     H     F     Cl                                                                                  ##STR110##   CH.sub.3                                   F     H     F     Cl  CO.sub.2 CHCHCH.sub.2                                                                        CH.sub.3                                   F     H     F     Cl  CO.sub.2 CH(CH.sub.3).sub.2                                                                  CH.sub.3                                   F     H     F     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   F     H     F     Cl  CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                       CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 CH(CH.sub.3).sub.2                                                                  CH.sub.3                                   Br    H     F     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.3                                   Br    H     F     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   Br    H     F     Cl  CO.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                           H                                          Br    H     F     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   OCH.sub.3                                                                            H     F     Cl  CO.sub.2 CH.sub.3                                                                            CH.sub.3                                   Br    H     F     Cl  CO.sub.2 CH.sub.2 CH.sub.3                                                                   CH.sub.3                                   OCH.sub.3                                                                            H     F     Cl  CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                           CH.sub.3                                   Cl    H     F     Cl                                                                                  ##STR111##   CH.sub.3                                   Br    H     F     Cl                                                                                  ##STR112##   CH.sub.3                                   Cl    H     F     Cl                                                                                  ##STR113##   CH.sub.3                                   Cl    H     F     Cl  CO.sub.2 CH.sub.2 CHCH.sub.2                                                                 CH.sub.3                                   Cl    H     H     H                                                                                   ##STR114##   CH.sub.3                                   Cl    H     H     Cl                                                                                  ##STR115##   CH.sub.3                                   Br    H     H     Cl                                                                                  ##STR116##   CH.sub.3                                   Br    H     F     Cl                                                                                  ##STR117##   CH.sub.3                                   OCH.sub.3                                                                            H     F     Cl                                                                                  ##STR118##   CH.sub.3                                   ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                          ##STR119##                                                                                                  melting                                          R.sup.1                                                                             R.sup.4                                                                              R.sup.5                                                                               R.sup.6     point °C.                                 ______________________________________                                         CH.sub.3                                                                            F     Cl     CO.sub.2 CH(CH.sub.3).sub.2                                                                95-99 [2R-Konfi-                                                               guration, [α].sub.D.sup.20 = -14,3                                       (c = 0,5 in CH.sub.3 OH)]                        CH.sub.3                                                                            F     Cl     CO.sub.2 CH(CH.sub.3).sub.2                                                                97-99 [2S-Konfi-                                                               guration, [α].sub.D.sup.20 = +13,8                                       (c = 0,5 in CH.sub.3 OH)]                        CH.sub.3                                                                            F     Cl                                                                                     ##STR120##                                                  CH.sub.3                                                                            F     Cl                                                                                     ##STR121##                                                  CH.sub.3                                                                            F     Cl     SCH.sub.2 CO.sub.2 CH.sub.3                                  CH.sub.3                                                                            F     Cl     OCH.sub.2 CHCH.sub.2                                         ______________________________________                                    

Formulations

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

    ______________________________________                                                    Weight Percent                                                                 Active                                                                         Ingredient                                                                              Diluent   Surfactant                                       ______________________________________                                         Wettable Powders                                                                            25-90       0-74     1-10                                         Oil Suspensions,                                                                             5-50      40-95     0-15                                         Emulsions, Solutions,                                                          (including Emulsifi-                                                           able Concentrates)                                                             Dusts         1-25      70-99     0-5                                          Granules, Baits                                                                             0.01-99       5-99.99                                                                               0-15                                         and Pellets                                                                    High Strength                                                                               90-99       0-10     0-2                                          Compositions                                                                   ______________________________________                                    

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books:, Caldwell, N.J. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. "McCutcheon's Detergents and Emulsifiers Annual", Allured Publ. Corp., Ridgewood, N.J, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc,, New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and usually grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example. Cross et al., "Pesticide Formulations", Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3.060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp 147-148, "Perry's Chemical Engineer's Handbook", 4th Ed., HcGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 32 46 493.

For further information regarding the art of formulation, see U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41: U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York. 1961, pp 81-96; and Hance et al., "Weed Control Handbook", 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways.

EXAMPLE A Wettable Powder

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         80%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  sodium alkylnaphthalenesulfonate                                                                          2%                                                  sodium ligninsulfonate     2%                                                  synthetic amorphous silica 3%                                                  kaolinite                  13%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended and packaged.

EXAMPLE B Wettable Powder

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         50%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  sodium alkylnaphthalenesulfonate                                                                          2%                                                  low viscosity methyl cellulose                                                                            2%                                                  diatomaceous earth         46%                                                 ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milled to produce Particles essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE C Granule

    ______________________________________                                         Wettable Powder of Example 8                                                                           5%                                                     attapulgite granules   95%                                                     (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                              ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE D Extruded Pellet

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         25%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  anhydrous sodium sulfate   10%                                                 crude calcium ligninsulfonate                                                                              5%                                                 sodium alkylnaphthalenesulfonate                                                                           1%                                                 calcium/magnesium bentonite                                                                               59%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE Low Strength Granule

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         1%                                                  7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  N,N-dimethylformamide      9%                                                  attapulgite granules       90%                                                 (U.S.S. 20 to 40 sieve)                                                        ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE F Granule

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         80%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  wetting agent              1%                                                  crude lingninsulfonate salt (containing                                                                   10%                                                 5-20% of the natural sugars)                                                   attapulgite clay           9%                                                  ______________________________________                                    

The ingredients are blended and milled to pass through a 0.15 mm (100 mesh) screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionall with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 1.4 mm-0.15 mm (14-100 mesh), and packaged for use.

EXAMPLE G Aqueous Suspension

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                          40%                                                7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  polyacrylic acid thickener   0.3%                                              dodecylphenol polyethylene glycol ether                                                                     0.5%                                              disodium phosphate           1%                                                monosodium phosphate         0.5%                                              polyvinyl alcohol            1.0%                                              water                       56.7%                                              ______________________________________                                    

The ingredients are blended and :ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE H High Strength Concentrate

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                          99%                                                7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  silica aerogel               0.5%                                              synthetic amorphous silica   0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE I Wettable Powder

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                          90%                                                7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  dioctyl sodium sulfosuccinate                                                                               0.1%                                              synthetic fine silica        9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen (0.3 mm) and then packaged.

EXAMPLE J Wettable Powder

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         40%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  sodium ligninsulfonate     20%                                                 montmorillonite clay       40%                                                 ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

EXAMPLE K Oil Suspension

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         35%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  blend of polyalcohol carboxylic                                                                            6%                                                 esters and oil soluble petroleum                                               sulfonates                                                                     xylene                     59%                                                 ______________________________________                                    

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

EXAMPLE L Dust

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         10%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  attapulgite                10%                                                 pyrophyllite               80%                                                 ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE M Oil Suspension

    ______________________________________                                         4-(4'-chloro-2'-fluoro-5'-carboisopropoxyphenyl)-                                                         25%                                                 7-chloro-3,5-dioxo-1,4-diazabicyclo-                                           [3.3.0]octane                                                                  polyoxyethylene sorbitol hexaoleate                                                                        5%                                                 highly aliphatic hydrocarbon oil                                                                          70%                                                 ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Utility

The compounds of the present invention are active herbicides. They have utility for broadspectrum preemergence and/or postemergence weed control in areas where complete control of all vegetation is desired, such as around industrial complexes, storage areas, parking lots, drive-in theaters, around billboards, fence rows, highway and railroad structures. Some of the compounds have utility for selective weed control in crops such as rice, wheat, barley, corn, soybeans, sugarbeets, cotton, peanut, all plantation crops including coffee, cocoa, sugarcane, oil palm, rubber, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple and conifers such as loblolly pine.

The compounds can be applied as a preemergence and/or postemergence treatment using techniques of banding, directed sprays or broadcast applications. The rates of application for the compounds of the invention are determined by a number of factors, including their use as selective or general herbicides, the crop species involved, the types-of weeds to be controlled, weather, climate, formulations selected, mode of application, amount of foliage present, etc. By selecting the appropriate rate which would be apparent to one skilled in the art, the compounds of this invention can be used in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, oil well sites, drive-in theaters, around billboards, highway and railroad structures and in fence rows. Alternatively, by selecting the proper rates and adjuvants, the compounds of this invention can be used for selective weeds control in peanuts and plantation corps such as citrus, sugarcane, coffee, oil palm, rubber, cocoa, grapes, fruit trees, nut trees, pineapple and banana. In general, the subject compounds are applied at levels of around 0.001 to 20 kg/ha, with a preferred rate range of 0.01 to 2 kg/ha rate. One skilled in the art can select the proper rates for a given situation.

The compounds of this invention may be used in combination with other herbicides listed below. They are particularly useful in combination with triazine, triazole, uracil, urea, amide, carbamate, bipyridylium, phenoxy, sulfonylurea and imidazole types for total vegetation control in plantation and other crops. The compounds may also be used in combination with mefluidide, glyphosate or gluphosinate.

A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control. Examples of other herbicides with which compounds of this invention can be formulated are: acetochlor, acifluorfen, acrolein, 2-propenal, alachlor, ametryn, amidosulfuron, ammonium sulfamate, amitrole, anilofos, asulam, atrazine, barban, benefin, bensulfuron methyl, bensulide, bentazon, benzofluor, benzoylprop, bifenox, bromacil, bromoxynil, bomoxynil heptanoate, bromoxynil octanoate, butachlor, buthidazole, buttalin, butylate, cacodylic acid, 2-chloro-N,N-di-2-propenylacetamide, 2-chloroallyl dlethyldithiocarbamate, chloramben, chlorbromuron. chloridazon, chlorimuron ethyl, chlormethoxynil, chlornitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodium, clomazone, cloproxydim, clopyralid, calcium salt or methylarsonic acid, cyanazine, cycloate, cyluron, cyperquat, cyprazine, cyprazole, cypromid, dalapon, dazomet, dimethyl 2,3,5,6-tetrachloro-1,4-benzenedicarboxylate, desmedipham, desmetryn, dicamba, dichlobenil, dichlorbrop, diclofop, diethatyl, difenzoquat, diflufenican, dimepiperate, dinitramine, dinoseb, diphenamid, diprobetryn, diquat, diuron, 2-methyl-4,6-dinitrophenol, disodium salt of methylarsonic acid, dymron, endothall, S-ethyl dipropylcarbamothioate, esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, fenac, fenoxaprop, fenuron, salt of fenuron and trichloroacetic acid, flamprop, fluazipop, fluazipop-P, fluchloralin, flumesulam, flumipropyn, fluometuron, fluorochloridone, fuorodifen, fluoroglycofen, flupoxam, fluridone, fluoroxypyr, fluzasulfuron, fomesafen, fosamine, glyphosate, haloxylop, hexaflurate, hexazinone, imazamethabenz, imazapyr, imazaquin, imazamethabenz methyl, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, karbutilate, lactofen, lenacil, linuron, metobenzuron, metsulfuron methyl, methylarsonic acid, monoammonium salt of methylarsonic acid, (4-chloro-2-methylphenoxy)acetic acid, S,S'-dimethyl-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarbothioate, mecoprop, mefenacet, mefluidide, methalbropalin, methabenzthiazuron, metham, methazole, methoxuron, metolachlor, metribuzin, 1,2-dihydropyridazine-3,6-dione, molinate, monolinuron, monuron, monuron salt and trichloroacetic acid, monosodium salt of methylarsonic acid, nabropamide, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorfen, norea, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, perfluidone, phenmedipham, picloram, 5-[2-chloro-4-(trifluormethyl)phenoxy]-2-nitroacetophenone oxime-0-acetic acid methyl ester, pretilachlor, brimisulfuron, brocyazine, profluralin, prometon, prometryn, pronamide, propachlor, propanil, propazine, propham, prosulfalin, prynachlor, pyrazolate, pyrazon, pyrazosulfuron ethyl, quinchlorac, quizalofop ethyl, rimsulfuron secbumeton, sethoxydim, siduron, simazine, 1-(a,a-dimethylbenzyl)-3-(4-methylphenyl)urea, sulfometuron methyl, trichloroacetic acid, tebuthiuron, terbacil, terbuchlor, terbuthylazine, terbutol, terbutryn, thifensulfuron methyl, thiobencarb, tri-allate, trialkoxydlm, triasulfuron, tribehuron methyl, triclopyr, tridiphane, trifluralin, trimeturon, (2,4-dichlorophenoxy)acetic acid, 4-(2,4-dichlorophenoxy)butanoic acid, vernolate, and xylachlor.

The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results are as follows:

    ______________________________________                                         Biological Tables                                                              ______________________________________                                          ##STR122##               compound 1                                            ##STR123##               compound 2                                            ##STR124##               compound 3                                            ##STR125##               compound 4                                            ##STR126##               compound 5                                            ##STR127##               compound 6                                            ##STR128##               compound 7                                            ##STR129##               compound 8                                            ##STR130##               compound 9                                            ##STR131##               compound 10                                           ##STR132##               compound 11                                           ##STR133##               compound 12                                           ##STR134##               compound 13                                           ##STR135##               compound 14                                           ##STR136##               compound 15                                           ##STR137##               compound 16                                           ##STR138##               compound 17                                           ##STR139##               compound 18                                           ##STR140##               compound 19                                           ##STR141##               compound 20                                           ##STR142##               compound 21                                           ##STR143##               compound 22                                           ##STR144##               compound 23                                           ##STR145##               compound 24                                           ##STR146##               compound 25                                           ##STR147##               compound 26                                           ##STR148##               compound 27                                           ##STR149##               compound 28                                           ##STR150##               compound 29                                          ______________________________________                                    

Test procedure

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli), giant foxtail (Setaria faberii), wild oats (Arena fatua), cheatgrass (Bromus secalinus), velvetleaf (Abutilon theophrasti), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum) and sorghum. Nutsedge tubers were planted and treated preemergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were visually rated for response to treatment and compared to controls. The ratings, summarized in Table A-E₄, are based on a numerical scale extending from 0=no injury, to 10=complete kill.

The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

B=burn

H=formative effect;

G=growth retardation:

E=emergence inhibition.

                                      TABLE A                                      __________________________________________________________________________     postemergence (application rate 2 kg a.i./ha)                                  __________________________________________________________________________             Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                              1   2   3   4   5   6   7   8   9   10  11  12                         __________________________________________________________________________     Barnyardgrass                                                                          1B  6B  8B  6B  10C 10C 10B 10C 8B  10  10  10                         Cheat grass                                                                            1B  1B  1B  2B  10C 10C 10B 10C 7B  10  10  10                         Cocklebur                                                                              --  4B  --  --  10C 10C --  10C --  10  10  10                         Morningglory                                                                           0.sup.                                                                             7B  6B  8B  10C 10C 10B 10C 9B  10  10  10                         Sorghum 1B  2B  2B  2B  10C 10C  9B 10C 4B  10  10  10                         Giant foxtail                                                                          1B  4B  7B  8B  10C 10C 10B 10C 9B  10  10  10                         Crabgrass                                                                              1B  6B  7B  3B  10C 10C 10B 10C 8B  10  10  10                         Velvetleaf                                                                             0.sup.                                                                             5B  8B  7B  10C 10C 10B 10C 8B  10  10  10                         Wild oats                                                                              1B  2B  2B  2B  10C 10C 10B 10C 6B  10  10  10                         __________________________________________________________________________                                         Comp. 13                                                                            Comp. 14                                                                            Comp. 15                                                                            Comp.                       __________________________________________________________________________                                                        16                                                      Barnyardgrass                                                                          10   10   10   10                                                      Cheat grass                                                                            10   10   10   10                                                      Cocklebur                                                                              10   10   10   10                                                      Morningglory                                                                           10   10   10   10                                                      Sorghum 10   10   10   10                                                      Giant foxtail                                                                          10   10   10   10                                                      Crabgrass                                                                              10   10   10   10                                                      Velvetleaf                                                                             10   10   10   10                                                      Wild oats                                                                              10   10   10   10                          __________________________________________________________________________

                                      TABLE B                                      __________________________________________________________________________     preemergence (application rate 2 kg a.i./ha)                                   __________________________________________________________________________             Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                              1   2   3   4   5   6   7   8   9   10  11  12                         __________________________________________________________________________     Barnyardgrass                                                                          0   8H, 2C                                                                             9H, 3C                                                                             9H, 3C                                                                             10C 10C 10C 10C 9C, 5H                                                                             10  10  10                         Cheat grass                                                                            0   0   5H, 1C                                                                             6G  10C 10C 10C 10C 3H  10  10  10                         Cocklebur                                                                              --  6H, 2C                                                                             --  --  10C 10C 10C 10C 0   10  10  10                         Morningglory                                                                           0   3G, 1C                                                                             2G, 1H                                                                             0   10C 10C 10C 10C 1C  10  10  10                         Sorghum 0   3H, 1C                                                                             5H, 1C                                                                             3G  10C 10C 10C 10C 0   10  10  10                         Giant foxtail                                                                          0   3H  10C 9H, 3C                                                                             10E 10E 10C 10C 10C 10  10  10                         Crabgrass                                                                              0   9H  10C 8H, 1C                                                                             10C 10C 10C 10C 9C  10  10  10                         Velvetleaf                                                                             0   10C 10C 9C  10E 10E 10E 10E 9C  10  10  10                         Wild oats                                                                              0   0   4H, 1C                                                                             4G, 2C                                                                             10C 10C 10C 10C 0   10  10  10                         __________________________________________________________________________                                         Comp. 13                                                                            Comp. 14                                                                            Comp. 15                                                                            Comp.                       __________________________________________________________________________                                                        16                                                      Barnyardgrass                                                                          10   10   10   10                                                      Cheat grass                                                                            10   10   10   10                                                      Cocklebur                                                                              10   10   10   10                                                      Morningglory                                                                           10   10   10   10                                                      Sorghum 10   10   10   10                                                      Giant foxtail                                                                          10   10   10   10                                                      Crabgrass                                                                              10   10   10   10                                                      Velvetleaf                                                                             10   10   10   10                                                      Wild oats                                                                              10   10   10   10                          __________________________________________________________________________

                                      TABLE C                                      __________________________________________________________________________     postemergence (application rate 0.2 kg a.i./ha)                                        Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                  17  18  19  20  21  22  23                                             __________________________________________________________________________     Corn    2B  2B  1B  0   1B  6B  2B                                             Wheat   3B  1B  0   0   2B  6B  2B                                             Barnyardgrass                                                                          5B  2B  1B  2B  1B  9B  4B                                             Cheat grass                                                                            3B  2B  0   0   1B  5B  3B                                             Cocklebur                                                                              2B  5B  0   0   1B  9B  3B                                             Morningglory                                                                           5B  6B  2B  1B  1B  10B 6B                                             Sorghum --  --  0   0   1B  --  3B                                             Giant foxtail                                                                          4B  3B  1B  1B  1B  7B  4B                                             Crabgrass                                                                              5B  2B  1B  1B  2Bb 8B  4B                                             Velvetleaf                                                                             3B  4B  1B  1B  1B  10B 4B                                             Wild oats                                                                              2B  1B  0   0   1B  5B  1B                                             __________________________________________________________________________

                                      TABLE D                                      __________________________________________________________________________     preemergence (application rate 0.2 kg a.i./ha)                                         Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                                              Comp.                                                  17  18  19  20  21  22  23                                             __________________________________________________________________________     Corn    0   0   0   0   0   2C  1G                                             Wheat   0   0   0   0   0   3C  0                                              Barnyardgrass                                                                          0   0   0   0   0   9H, 5C                                                                             1H                                             Cheat grass                                                                            0   0   0   0   0   5C  0                                              Cocklebur                                                                              0   0   0   0   0   7G  0                                              Morningglory                                                                           0   0   0   0   0   3H, 2C                                                                             3G                                             Sorghum 0   0   0   0   0   5G, 2C                                                                             0                                              Giant foxtail                                                                          1H  0   0   2G  0   10H 1H                                             Crabgrass                                                                              4G  0   0   2G  0   10H 0                                              Velvetleaf                                                                             0   0   0   0   0   9C  0                                              Wild oats                                                                              0   0   0   0   0   6C  0                                              __________________________________________________________________________

                  TABLE E.sub.1                                                    ______________________________________                                         postemergence (rate 200 g/ha)                                                              Comp. Comp.    Comp.   Comp.                                                   26    27       28      29                                          ______________________________________                                         Barley        2B      2B       3B     9B                                       Barnyardgrass 4B      1B       2B    10B                                       Bedstraw      10B     3B       5B    10B                                       Blackgrass    2B      1B       3B     9B                                       Cheatgrass    2B      1B       3B    --                                        Chickweed     6B      3B       --     9B                                       Cocklebur     9B      1B       4B    10B                                       Corn          2B      2B       3B     8B                                       Cotton        100B    9B       9B    10B                                       Crabgrass     3B      2B       2B    10B                                       Downy brome   --      --       --     9B                                       Giant foxtail 3B      3B       3B     9B                                       Lambsquarter  8B      2B       7B    10B                                       Morningglory  10B     2B       5B    10B                                       Nutsedge      3B      0.sup.   1B     6B                                       Rape          10B     2B       2B    10B                                       Rice          5B      3B       3B    10B                                       Sorghum       3B      3B       4B    10B                                       Soybean       6B      2B       7B    10B                                       Sugar beet    10B     2B       6B    10B                                       Velvetleaf    3B      5G       3B    10B                                       Wheat         4B      0.sup.   3B     9B                                       Wild buckwheat                                                                               10B     1B       6B    10B                                       Wild oat      2B      2B       2B    10B                                       ______________________________________                                    

                  TABLE E.sub.2                                                    ______________________________________                                         preemergence (rate 200 g/ha)                                                               Comp.  Comp.    Comp.    Comp.                                                 26     27       28       29                                        ______________________________________                                         Barley         0       0         0      5C                                     Barnyardgrass  1H      3G        0     10C                                     Bedstraw       9       2G       10C    10C                                     Blackgrass     0       0         1C     9C                                     Cheatgrass     8G      0         1C    --                                      Chickweed     10C      0         0     10E                                     Cocklebur      0       0         0      7G                                     Corn           0       2G        2G     8H                                     Cotton         0       0         0     10C                                     Crabgrass      2H      1H        5G    10C                                     Downy brome   --       --       --     10C                                     Giant foxtail  0       3G        4G    10C                                     Lambsquarter  10C      5G       10C    10E                                     Morningglory   0       0         0     10C                                     Nutsedge       0       0         0      4C                                     Rape           0       1H        2G    10E                                     Rice           2G      0         0      7G                                     Sorghum        0       0         0      9C                                     Soybean        0       0         0      9H                                     Sugar beet     0       1H        9C    10C                                     Velvetleaf    10C      0         0     10C                                     Wheat          2C      0         0      7C                                     Wild buckwheat                                                                               10C      0        10C    10E                                     Wild oat       2G      0         0      9C                                     ______________________________________                                    

                  TABLE E.sub.3                                                    ______________________________________                                         postemergence (rate 50 g/ha)                                                               Comp.  Comp.    Comp.    Comp.                                                 26     27       28       29                                        ______________________________________                                         Barley         2B      0        1B      9B                                     Barnyardgrass  3B      1B       1B      9B                                     Bedstraw       8B      1B       1B     10B                                     Blackgrass     1B      0        1B      7B                                     Cheatgrass     1B      1B       1B     --                                      Chickweed      3B      1B       1B      9B                                     Cocklebur      7B      1B       1B     10B                                     Corn           2B      1B       1B      8B                                     Cotton        10       1B       8B     10B                                     Crabgrass      2B      1B       1B      8B                                     Downy brome   --       --       --      6B                                     Giant foxtail  2B      1B       1B      8B                                     Lambsquarter   7B      1B       4B     10B                                     Morningglory   9B      1B       1B     10B                                     Nutsedge       1B      0        0       3B                                     Rape          10B      0        2B     10B                                     Rice           2B      1B       3B      9B                                     Sorghum        2B      1B       2B      9H                                     Soybean        8B      1B       3B     10B                                     Sugar beet     9B      0        1B     10B                                     Velvetleaf     2B      2B       1B     10B                                     Wheat          3B      0        1B      8B                                     Wild buckwheat                                                                               10B      1B       2B     10B                                     Wild oat       2B      0        1B      7B                                     ______________________________________                                    

                  TABLE E.sub.4                                                    ______________________________________                                         preemergence (rate 50 g/ha)                                                                Comp.  Comp.    Comp.    Comp.                                                 26     27       28       29                                        ______________________________________                                         Barley         0       0        0       5G                                     Barnyardgrass  0       0        0      10C                                     Bedstraw       3G      0        0      10C                                     Blackgrass     0       0        0       9C                                     Cheatgrass     0       0        0      --                                      Chickweed      0       0        0      10E                                     Cocklebur      0       0        0      --                                      Corn           0       0        0       8H                                     Cotton         0       0        0       8H                                     Crabgrass      2H      0        0      10C                                     Downy brome   --       --       --      9C                                     Giant foxtail  0       0        0      10C                                     Lambsquarter  10C      --       2G     10E                                     Morningglory   0       0        0       9H                                     Nutsedge       0       0        0       6C                                     Rape           0       0        0      10E                                     Rice           0       0        0       7G                                     Sorghum        0       0        0       8H                                     Soybean        0       0        0       9H                                     Sugar beet     0       --       0       9C                                     Velvetleaf     2G      0        0      10C                                     Wheat          0       0        0       5G                                     Wild buckwheat                                                                                5G      0        --      9C                                     Wild oat       0       0        0       9C                                     ______________________________________                                    

Test B

Plastic tray liners with individual planting compartments were filled with planting medium and seeded separately with dallisgrass (Pasoalum dilatatum), bermudagrass (Cynodon dactylon), annual bluegrass (Poa annum), guineagrass (Panicum maximum), broadleaf signalgrass (Brachiaria platyphylla), goosegrass (Eleusine indicia), large crabgrass (Digitaria sanguinalis), smooth crabgrass (D. ischaemum), sandbur (Cenchrus echinatus), itchgrass (Rottboellia cochinchinensis), Texas panicum (P. texanum), Johnson grass (Sorghum halepense), alfalfa (Medicago sativa), peanut (Arachis hypogea), morningglory (Ipomea sp.), ragweed (Ambrosia elatior), putslane (portulaca oleracea) and Pueraris javanica. Tubers of purple nutsedge (Cyperus rotundus) and yellow nutsedge (C. esculentus) were also planted separately in individual pots.

The plantings were staggered so that the preemergence and postemergence treatments with the compounds formulated in an non-phytotoxic spray solution were applied on the same day. Plants were visually rated compared with the appropriate controls at the end of the test. The injuring ratings were based on the scale of 0 to 100 where 0 indicates no effect, 20 indicates minimal effect and 100 indicates complete control. The variations in the results for the same compound could be due to the fact that the tests were conducted at different times of the year and on plants at different growth stages. The results are shown in Tables E_(a) -E₁.

                  TABLE E.sub.a                                                    ______________________________________                                                       Compound 4                                                                     250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     0           0                                                  Bermudagrass    0           0                                                  Annual bluegrass                                                                               0           0                                                  Guineagrass     0           0                                                  Broadleaf signalgrass                                                                          0           0                                                  Goosegrass      0           0                                                  Large crabgrass 0           0                                                  Smooth crabgrass                                                                               0           0                                                  Sandbur         0           0                                                  Itchgrass       0           0                                                  Johnson grass   0           0                                                  Morningglory    0           0                                                  Ragweed         0           0                                                  Purslane        0           0                                                  Alfalfa         0           0                                                  Peanut          0           0                                                  Purple nutsedge 0           0                                                  Yellow nutsedge 0           0                                                  ______________________________________                                    

                  TABLE E.sub.b                                                    ______________________________________                                                    Compound 6                                                                     500  250    125    500  250  125 g/ha                                          Preemergence                                                                              Postemergence                                            ______________________________________                                         Dallisgrass  100    100    100  100  100  100                                  Bermudagrass 100    100    100  70   100  70                                   Annual bluegrass                                                                            100    100    100  50   50   50                                   Guineagrass  100    100    100  80   50   40                                   Broadleaf signalgrass                                                                       100    100    90   50   60   60                                   Goosegrass   100    100    100  100  90   90                                   Large crabgrass                                                                             100    100    100  100  90   90                                   Smooth crabgrass                                                                            100    100    100  90   60   50                                   Sandbur      100    100    100  100  90   70                                   Itchgrass    100    100    80   70   50   30                                   Texas panicum                                                                               100    100    100  100  80   50                                   Johnson grass                                                                               100    100    80   30   30   20                                   Morningglory 100    100    90   100  100  100                                  Purslane     100    100    100  100  100  100                                  Alfalfa      100    100    100  100  100  100                                  Peanut       0      0      0    70   30   20                                   ______________________________________                                    

                  TABLE E.sub.c                                                    ______________________________________                                                       Compound 6                                                                     250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         90                                                 Bermudagrass    100         40                                                 Annual bluegrass                                                                               100         20                                                 Guineagrass     100         60                                                 Broadleaf signalgrass                                                                          100         30                                                 Goosegrass      100         80                                                 Large crabgrass 100         90                                                 Smooth crabgrass                                                                               100         50                                                 Sandbur          90         100                                                Itchgrass       100         20                                                 Johnson grass   100         20                                                 Morningglory    100         100                                                Ragweed         100         100                                                Purslane        100         80                                                 Alfalfa         100         100                                                Peanut           0          30                                                 ______________________________________                                    

                  TABLE E.sub.d                                                    ______________________________________                                                       Compound 6                                                                     250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         90                                                 Bermudagrass    100         50                                                 Annual bluegrass                                                                               100         70                                                 Guineagrass     100         30                                                 Broadleaf signalgrass                                                                          100         30                                                 Goosegrass      100         80                                                 Large crabgrass 100         70                                                 Smooth crabgrass                                                                               100         50                                                 Sandbur         100         60                                                 Itchgrass       100         30                                                 Johnson grass   100         20                                                 Morningglory     80         100                                                Ragweed         100         100                                                Purslane        100         90                                                 Alfalfa         100         100                                                Peanut           0          70                                                 Purple nutsedge  40         20                                                 Yellow nutsedge  80         80                                                 ______________________________________                                    

                  TABLE E.sub.e                                                    ______________________________________                                                       Compound 7                                                                     250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         20                                                 Bermudagrass    100          0                                                 Annual bluegrass                                                                                80         90                                                 Guineagrass     100          0                                                 Broadleaf signalgrass                                                                          100          0                                                 Goosegrass      100          0                                                 Large crabgrass 100          0                                                 Smooth crabgrass                                                                               100          0                                                 Sandbur          90          0                                                 Itchgrass        70          0                                                 Johnson grass    60          0                                                 Morningglory     80         100                                                Ragweed         100         100                                                Purslane        100         100                                                Alfalfa          90         100                                                Peanut           20         60                                                 Purple nutsedge  0          20                                                 Yellow nutsedge  10         50                                                 ______________________________________                                    

                  TABLE E.sub.f                                                    ______________________________________                                                       Compound 11                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         100                                                Bermudagrass    100         80                                                 Annual bluegrass                                                                               100         60                                                 Guineagrass     100         70                                                 Broadleaf signalgrass                                                                          100         80                                                 Goosegrass      100         80                                                 Large crabgrass 100         80                                                 Smooth crabgrass                                                                               100         60                                                 Sandbur         100         80                                                 Itchgrass       100         100                                                Johnson grass   100         100                                                Morningglory    100         100                                                Ragweed         100         100                                                Purslane        100         90                                                 Alfalfa         100         100                                                Peanut           60         100                                                Purple nutsedge  20         30                                                 Yellow nutsedge  80         100                                                ______________________________________                                    

                  TABLE E.sub.g                                                    ______________________________________                                                       Compound 12                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     90          20                                                 Bermudagrass    20          0                                                  Annual bluegrass                                                                                0          0                                                  Guineagrass     80          0                                                  Broadleaf signalgrass                                                                           0          0                                                  Goosegrass      100         0                                                  Large crabgrass 90          0                                                  Smooth crabgrass                                                                               50          0                                                  Sandbur         60          0                                                  Itchgrass       20          0                                                  Johnson grass   80          0                                                  Morningglory    50          20                                                 Ragweed         30          20                                                 Purslane        100         20                                                 Alfalfa         90          0                                                  Peanut          20          0                                                  Purple nutsedge  0          0                                                  Yellow nutsedge  0          0                                                  ______________________________________                                    

                  TABLE E.sub.h                                                    ______________________________________                                                       Compound 13                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         0                                                  Bermudagrass    30          0                                                  Annual bluegrass                                                                               30          0                                                  Guineagrass     90          0                                                  Broadleaf signalgrass                                                                          20          0                                                  Goosegrass      100         0                                                  Large crabgrass 70          0                                                  Smooth crabgrass                                                                               90          0                                                  Sandbur         30          0                                                  Itchgrass       20          0                                                  Johnson grass   80          0                                                  Morningglory    40          0                                                  Ragweed         70          0                                                  Purslane        100         30                                                 Alfalfa         40          0                                                  Peanut           0          0                                                  Purple nutsedge  0          0                                                  Yellow nutsedge  0          0                                                  ______________________________________                                    

                  TABLE E.sub.i                                                    ______________________________________                                                       Compound 14                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         100                                                Bermudagrass    100         60                                                 Annual bluegrass                                                                               100         70                                                 Guineagrass     100         70                                                 Broadleaf signalgrass                                                                          100         60                                                 Goosegrass      100         80                                                 Large crabgrass 100         70                                                 Smooth crabgrass                                                                               100         50                                                 Sandbur         100         100                                                Itchgrass       100         70                                                 Johnson grass   100         50                                                 Morningglory    100         100                                                Ragweed         100         100                                                Purslane        100         90                                                 Alfalfa         100         100                                                Peanut           50         100                                                Purple nutsedge  40         50                                                 Yellow nutsedge  80         100                                                ______________________________________                                    

                  TABLE E.sub.j                                                    ______________________________________                                                       Compound 22                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     90          0                                                  Bermudagrass    90          0                                                  Annual bluegrass                                                                               70          0                                                  Guineagrass     100         0                                                  Broadleaf signalgrass                                                                          90          0                                                  Goosegrass      100         0                                                  Large crabgrass 100         0                                                  Smooth crabgrass                                                                               90          0                                                  Sandbur         90          0                                                  Itchgrass       100         0                                                  Johnson grass   50          0                                                  Morningglory    80          60                                                 Ragweed         100         70                                                 Purslane        100         90                                                 Alfalfa         60          90                                                 Peanut          20          30                                                 Purple nutsedge  0          0                                                  Yellow nutsedge  0          0                                                  ______________________________________                                    

                  TABLE E.sub.k                                                    ______________________________________                                                       Compound 24                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         90                                                 Bermudagrass    100         50                                                 Annual bluegrass                                                                               100         50                                                 Guineagrass     100         70                                                 Broadleaf signalgrass                                                                          100         30                                                 Goosegrass      100         80                                                 Large crabgrass 100         60                                                 Smooth crabgrass                                                                               100         50                                                 Sandbur         100         80                                                 Itchgrass       100         50                                                 Johnson grass   100         50                                                 Morningglory    100         100                                                Ragweed         100         100                                                Purslane        100         90                                                 Alfalfa         100         100                                                Peanut           60         100                                                Purple nutsedge  60         20                                                 Yellow nutsedge  70         100                                                ______________________________________                                    

                  TABLE E.sub.l                                                    ______________________________________                                                       Compound 25                                                                    250       250 g/ha                                                             Preemergence                                                                             Postemergence                                          ______________________________________                                         Dallisgrass     100         100                                                Bermudagrass    100         20                                                 Annual bluegrass                                                                               100          0                                                 Guineagrass     100         40                                                 Broadleaf signalgrass                                                                          100         40                                                 Goosegrass      100         30                                                 Large crabgrass 100         50                                                 Smooth crabgrass                                                                               100         20                                                 Sandbur         100         20                                                 Itchgrass       100         60                                                 Johnson grass   100         20                                                 Morningglory    100         80                                                 Ragweed         100         100                                                Purslane        100         90                                                 Alfalfa         100         100                                                Peanut           60         70                                                 Purple nutsedge  0          20                                                 Yellow nutsedge  60         30                                                 ______________________________________                                    

Test C

Windowsill flats were filled with planting medium and seeded with peanut (A. hypogea), gaint foxtail (Setari faberi), large crabgrass (D. Sanguinalis), guineagrass (P. maximum), Johnson grass (S. haliebense), nightshade (solanum nigrum), morningglory (Ipomes sp.) and velvetleaf (Abutilon theophrasti). The plantings were treated preemergence with Compound 6 formulated in a non-phytotoxic spray solution. Planets were visually rated 21 and 40 days-after-treatment (DAT) and compared with the appropriate controls. The injuring ratings were based on the scale use in Test B. The results are shown in Table F.

Test D

Plastic tray liners with individual planting compartments were filled with planting medium and seeded with corn (Zea mays), soybean (Glycine max.), peanut (A. hypogea), tomato (Lycopersium esenlentum), gaint foxtail (S. faberi), guineagrass (P. maximum), Johnson grass (S. halepense), velvetleaf (A. theophrasti), morningglory, nightshade varieties--Solanum nigrum, S. nigrum subsp. nigrum. S. ptycanthus (green berries and black berries), S. nigrum subsp. schetesii and S. nigrum (atrazine tolerant).

The plantings were treated preemergence with Compound 6 formulated in a non-phytotoxic spray solution. Plants were visually rated at the enid of the test and compared with the appropriate controls. The injury ratings used in Test 8 were also employed in this test. The results are shown in Table G.

Test E

Rooted rough lemon cuttings were planted in 15-cm plastic pots. Another set of 11-cm plastic pots were filled with planting medium were seeded with balsam apple wine (Momordica charantia). sandbur (C. echinatus), pigweed (Amaranthus viridus) and guineagrass (P. maximum).

This citrus was sprayed to simulate the trunk-to-trunk herbicide application method used in citrus groves, the weeds were treated preemergence and the balsam apple wine treated both preemergence and postemergence. All pots were treated with Compound 6 formulated in a non-phytotoxic spray solvent. Plants were visually rated 21 and 65 DAT and compared with appropriate controls. The injury rating scale used in Test B was also used. The results are shown in Table H.

                  TABLE F                                                          ______________________________________                                                     Compound 6                                                                     250  125        64     g/ha                                        Species       Preemergence                                                     ______________________________________                                                     21 DAT                                                             Peanut         60     20        0                                              Giant foxtail 100    100        100                                            Large crabgrass                                                                              100    100        100                                            Guineagrass   100    100        100                                            Johnson grass 100    100        100                                            Nightshade    100    100        100                                            Morningglory  100    100        80                                             Velvetleaf    100    100        100                                                        40 DAT                                                             Peanut         40     20        0                                              Giant foxtail 100    100        100                                            Large crabgrass                                                                              100    100        100                                            Guineagrass   100    100        100                                            Johnson grass 100    100        90                                             Nightshade    100    100        100                                            Morningglory  100    100        80                                             Velvetleaf    100    100        100                                            ______________________________________                                    

                  TABLE G                                                          ______________________________________                                                      Compound 6                                                                     64   32     16     8    4    g/ha                                 Species        Preemergence                                                    ______________________________________                                         Corn           60     60     10   0    0                                       Soybean        70     40     0    0    0                                       Peanut         20     0      0    0    0                                       Tomato         100    100    100  100  90                                      Giant foxtail  100    100    100  90   40                                      Guineagrass    100    100    80   80   60                                      Johnson rass   100    90     30   20   20                                      Velvetleaf     100    100    100  100  100                                     Morningglory   50     30     20   0    0                                       Solanum nigrum 100    100    100  100  100                                     S. nigrum      100    100    100  100  100                                     S. nigrum subsp. nigrum                                                                       100    100    100  100  100                                     S. ptycanthus (green                                                                          100    100    100  100  100                                     berries)                                                                       S. nigrum subsp. schetesii                                                                    100    100    100  100  100                                     S. ptycanthus (black                                                                          100    100    100  100  100                                     berries)                                                                       S. nigrum (atrazine                                                                           100    100    100  100  100                                     tolerant)                                                                      ______________________________________                                    

                  TABLE H                                                          ______________________________________                                                       Compound 6                                                                     500  250    125    64   g a.i./ha                                ______________________________________                                                       21 DAT                                                           Post directed   0      0      0    0                                           Citrus (rough lemon)                                                           Preemergence                                                                   Balsam apple vine                                                                              100    100    100  100                                         Sandbur         100    100    100  100                                         Pigweed         100    100    100  100                                         Guineagrass     100    100    100  100                                         Postemergence   100    100    100  100                                         Balsam apple vine                                                                            65 DAT                                                           Post directed   0      0      0    0                                           Citrus (rough lemon)                                                           Preemergence                                                                   Balsam apple vine                                                                              100    100    100  100                                         Sandbur         100    100    100  100                                         Pigweed         100    100    100  100                                         Guineagrass     100    100    100  100                                         Postemergence   100    100    100  100                                         Balsam apple vine                                                              ______________________________________                                     

What is claimed is:
 1. A bicyclic imide of formula I ##STR151## wherein the bond linking C-7 and C-8 may be single or double; m is 1-7;R^(A) can occupy one or more of the 2 or 6-8 positions and is independently selected from the group: hydroxy, halogen CN OR³, (C₁ -C₄) alkyl, S(O)_(n) R³, COR³, and C(O)SR³ ; Q is ##STR152## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈) alkoxyalkyl, (C₂ -C₄)carboxy alkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈)trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O)(OR¹⁷)₂, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy; R⁴ is hydrogen or halogen; R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ; R⁶ is hydrogen, (C₁ -C₈)alkyl, (C₁ -C₈)haloalkyl, halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, (O)SR¹⁰, C(O)NR¹¹ R¹², CHO, CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NO₂, CN, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ; R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O; R¹⁰ is (C₁ -C₈)alkyl, (C₃ -C₈) cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, (C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ P(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(OR¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R¹², CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalky; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy; R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl; R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy; R¹¹ and R¹² may be taken together as --(CH₂)₅ --, or --(CH₂)₄ --, in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl; R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C.sub.[)cycloalkyl; R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl; R¹⁶ is hydrogen or (C₁ -C₃)alkyl; R¹⁷ is (C₁ -C₆)alkyl, (C₃ -C₆)alkenyl Or (C₃ -C₆)alkynyl; W is 0 or S; n is 0, 1 or 2;provided that when Q is not fused to a ring bridging the 5'- and 6'-position and C-7 and C-8 are linked by a single bond, then at least one R^(A) is other than hydroxy, halogen, (C₁ -C₄)alkyl, (C₁ -C₄) alkoxy.
 2. A bicyclic imide selected from the group consisting of 4-[4'-chloro-2'-fluoro-5'-(prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazobicyclo-[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(2-propynyloxy)phenyl]-3,5-dioxo-7-chloro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methylethoxy)phenyl]-3,5-dioxo-7,7-difluoro-1,4-diazabicyclo[3.3.0]octane and any stereoisomer thereof.
 3. A bicyclic imide according to claim 1 or 2, characterized in that at least one R^(A) is in the 7-position.
 4. A bicyclic imide according to claim 3, characterized in that at least one R^(A) in the 7-position is fluoro, chloro or bromo.
 5. A bicyclic imide according to any one of claims 1 to 4, characterized in that it has 2R-configuration.
 6. A composition for controlling weeds comprising an effective amount of a compound of claim 1 or 2 and at least one carrier therefor.
 7. A method for controlling weeds comprising applying to the locus to be protected an effective amount of a compound of claim 1 or
 2. 8. A method for controlling weeds in plantation crops comprising applying to the locus to be protected an effective amount of a compound of formula Ia: ##STR153## wherein the bond linking C-7 and C-8 may be single or double; m is 1-7;R^(A) can occupy one or more of the 2 or 6-8 positions and is independently selected from the group: hydroxy, halogen, CN, OR³, (C₁ -C₄)alkyl, S(O)_(n) R³, COR³, and C(O)SR³ ; Q is ##STR154## wherein R³ is (C₁ -C₈)alkyl, (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₄)carboxy alkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₃ -C₈)trialkylsilyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)haloalkenyl, (C₃ -C₈)haloalkynyl, (C₂ -C₈)alkylcarbonyl, (C₂ -C₈)alkoxycarbonyl, (C₂ -C₈)haloalkoxycarbonyl, P(O))(OR¹⁷)₂, CHR¹⁶ P(O)(OR¹⁷)₂ or CHR¹⁶ P(S)(OR¹⁷)₂, phenyl or benzyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy; R⁴ is hydrogen or halogen; R⁵ is (C₁ -C₂)alkyl, (C₁ -C₂)haloalkyl, OCH₃, SCH₃, OCHF₂, halogen, CN or NO₂ ; R⁶ i s hydrogen, (C₁ -C₈)alkyl, (C₁ -C₈)haloalkyl, halogen, OR¹⁰, S(O)_(n) R¹⁰, COR¹⁰, C(O)SR¹⁰, C(O)NR¹¹ R¹², CHO CH═CHCO₂ R¹⁰, CO₂ N═CR¹³ R¹⁴, NO₂, CN, NHSO₂ R¹⁵ or NHSO₂ NHR¹⁵ ; R⁷ and R⁸ are independently hydrogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or halogen; when Q is Q-2 or Q-6, R⁷ and R⁸ together with the carbon to which they are attached may be C═O; R¹⁰ is (C₁ -C₈)alkyl (C₃ -C₈)cycloalkyl, (C₃ -C₈)alkenyl, (C₃ -C₈)alkynyl, (C₁ -C₈)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₂ -C₆)alkylthioalkyl, (C₂ -C₈)alkylsulfinylalkyl, (C₂ -C₈)alkylsulfonylalkyl, (C₃ -C₈)alkoxyalkoxyalkyl, (C₄ -C₈)cycloalkylalkyl, (C₂ -C₄)carboxyalkyl, (C₃ -C₈)alkoxycarbonylalkyl, (C₆ -C₈)alkenyloxycarbonylalkyl, (C₆ -C₈)alkynyloxycarbonylalkyl, (C₆ -C₈)cycloalkoxyalkyl, (C₄ -C₈)alkenyloxyalkyl, (C₄ -C₈)alkynyloxyalkyl, (C₃ -C₈)haloalkoxyalkyl, (C₄ -C₈)haloalkenyloxyalkyl, (C₄ -C₈)haloalkynyloxyalkyl, (C₆ -C₈)cycloalkylthioalkyl, (C₄ -C₈)alkenylthioalkyl, (C₄ -C₈)alkynylthioalkyl, (C₄ -C₈)trialkylsilylalkyl, (C₃ -C₈)cyanoalkyl, (C₃ -C₈)halocycloalkyl, (C₃ -C₈)haloalkenyl, (C₅ -C₈)alkoxyalkenyl, (C₅ -C₈)haloalkoxyalkenyl, (C₅ -C₈)alkylthioalkenyl, (C₃ -C₈)haloalkynyl, (C₅ -C₈)alkoxyalkynyl, ](C₅ -C₈)haloalkoxyalkynyl, (C₅ -C₈)alkylthioalkynyl, (C₂ -C₈)alkylcarbonyl, CHR¹⁶ COR¹⁷, CHR¹⁶ P(O)(OR¹⁷)₂, P(O)(OR¹⁷)₂, CHR¹⁶ P(S)(O)R¹⁷)₂, CHR¹⁶ C(O)NR¹¹ R12, CHR¹⁶ C(O)NH₂, (C₁ -C₄)alkyl substituted with phenoxy or benzyloxy optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; benzyl optionally substituted with halogen, (C₁ -C₃)alkyl or (C₁ -C₃)haloalkyl; or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl Or (C₁ -C₄)alkoxy; R¹¹ and R¹³ are independently hydrogen or (C₁ -C₄)alkyl; R¹² and R¹⁴ are independently (C₁ -C₄)alkyl, or phenyl optionally substituted with halogen, (C₁ -C₃)alkyl, (C₁ -C₃)haloalkyl or (C₁ -C₄)alkoxy; R¹¹ and R¹² may be taken together as --(CH₂)₅ --, or --(CH₂)₄ -- in which optionally one or more H-atoms may be replaced by (C₁ -C₃)alkyl, phenyl or benzyl; R¹³ and R¹⁴ may be taken together with the carbon to which they are attached to form (C₃ -C₈)cycloalkyl; R¹⁵ is (C₁ -C₄)alkyl or (C₁ -C₄)haloalkyl; R¹⁶ is hydrogen or (C₁ -C₃)alkyl; R¹⁷ is (C₁ -C₆)alkyl, (C₃ -C₆)alkenyl or (C₃ -C₆)alkynyl; W is 0 or S; n is 0, 1 or
 2. 9. A method of claim 8 wherein the plantation crop is selected from the group consisting of citrus, sugarcane, coffee, banana, oil palm, grapes and rubber.
 10. A method of claim 8 or 9 employing at least one of the compounds of the group consisting of 4-[4'-chloro-2'-fluoro-5'-(1-methylethoxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(prop-2-ynyloxy)phenyl]-3,5-dioxo-7-fluoro-1,4-diazabicyclo[3.3.0]octane, 4-[4'-chloro-2'-fluoro-5'-(1-methyl-ethoxy)phenyl]-3,5-dioxo-7,7-difluoro-1,4-diazabicyclo[3.3.0]octane, 6-fluoro-2-(7-fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-tetrahydropyrrolo[1,2-c]imidazole-1,3-dione, 6,6-difluoro-2-(7-fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-tetrahydropyrrolo[1,2-c]imidazole-1,3-dione (JUPAC), 4-[2-chloro-4-fluoro-5-(6-fluoro-1,3-dioxotetrahydropyrrolo[1,2-c]imidazol-2-yl)phenoxy]but-2-enoic acid methyl ester (JUPAC) and any stereoisomer thereof.
 11. A method of claim 8 wherein the crop is peanut and the compound is applied preemergence. 